U.S. patent number 5,983,647 [Application Number 08/682,677] was granted by the patent office on 1999-11-16 for foamed thermal insulating material and insulated structure.
This patent grant is currently assigned to Matsushita Refrigeration Company. Invention is credited to Hideo Nakamoto, Tomohisa Tenra, Yoshiyuki Tsuda, Kazutaka Uekado.
United States Patent |
5,983,647 |
Uekado , et al. |
November 16, 1999 |
Foamed thermal insulating material and insulated structure
Abstract
An insulated structure is formed by injection of a foamed
thermal-insulating material created by foaming into a space between
a plastic board and metal plate with a disposition of copper pipes.
A non-halogenated organophosphorus compound having a molecular
weight over 150 as an additive with an OH group as a functional
group is mixed with the raw materials of the foamed
thermal-insulating material including polyol, a foam stabilizer, a
catalyst, a foaming agent having at least one component of
hydrocarbon, and an organic polyisocyanates. By adding a
non-halogenated organophosphorus compound, which has a molecular
weight over 150 as an additive with an OH group as a functional
group, the burning rate of the foamed thermal-insulating material
becomes the same as that of the foamed thermal-insulating material
which uses CFC11 as a foaming agent. Also, the possibilities of
phosphor corrosion by free ionization to copper pipes, which are
disposed inside of the insulated structure, are eliminated and
phosphorus transfer to the plastic board and worries of food
contamination are also eliminated.
Inventors: |
Uekado; Kazutaka (Hyogo,
JP), Tsuda; Yoshiyuki (Osaka, JP),
Nakamoto; Hideo (Osaka, JP), Tenra; Tomohisa
(Osaka, JP) |
Assignee: |
Matsushita Refrigeration
Company (Osaka, JP)
|
Family
ID: |
37708150 |
Appl.
No.: |
08/682,677 |
Filed: |
July 24, 1996 |
PCT
Filed: |
November 24, 1994 |
PCT No.: |
PCT/JP94/01984 |
371
Date: |
July 24, 1996 |
102(e)
Date: |
July 24, 1996 |
PCT
Pub. No.: |
WO96/16098 |
PCT
Pub. Date: |
May 30, 1996 |
Current U.S.
Class: |
62/45.1; 312/400;
312/401; 62/440; 62/451 |
Current CPC
Class: |
F25D
23/061 (20130101); C08G 18/3878 (20130101); C08G
18/8083 (20130101); F16L 59/02 (20130101); F25D
23/064 (20130101); C08G 18/288 (20130101); C08G
2101/00 (20130101); C08G 2110/005 (20210101); C08G
2110/0025 (20210101); F25D 2201/126 (20130101) |
Current International
Class: |
C08G
18/80 (20060101); C08G 18/28 (20060101); C08G
18/38 (20060101); F16L 59/02 (20060101); F25D
23/06 (20060101); C08G 18/00 (20060101); F17C
011/00 (); F25D 011/00 (); F25D 023/06 (); A47B
096/04 () |
Field of
Search: |
;62/451,440,430,45.1
;428/304.4 ;521/163,137,400,401 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
4684475 |
August 1987 |
Matulewicz |
5073283 |
December 1991 |
Goddard et al. |
5100927 |
March 1992 |
Tmano et al. |
5247807 |
September 1993 |
Jarman et al. |
5397810 |
March 1995 |
Ozaki et al. |
5600019 |
February 1997 |
Bhattacharjee et al. |
|
Primary Examiner: MacMillan; Keith D.
Assistant Examiner: Ricigliano; Joseph W.
Attorney, Agent or Firm: Wood, Phillips, VanSanten, Clark
& Mortimer
Parent Case Text
This application is a .sctn.371 of Application No. PCT/JP94/01984,
filed Nov. 24, 1994.
Claims
We claim:
1. An insulated structure comprising:
a) a first housing defining an insulated storage area;
b) a second housing spaced from and generally conforming to the
shape of the first housing, the first housing and second housing
defining a first spacial area;
c) a foamed thermal-insulating material created by foaming injected
into the first spacial area, the foamed thermal insulating material
comprising:
i) polyol;
ii) a foam stabilizer;
iii) a catalyst comprising: a first tertiary amine polymer; and a
second tertiary amine polymer with over 50% by weight of a catalyst
component being partially or entirely neutralized by carboxylic
acid;
iv) a foaming agent having at least one component of
hydrocarbon;
v) an isocynate component comprising organic polyisocynates;
and
vi) a non-halogenated organophosphorous compound; and
d) a copper pipe having refrigerant circulating therein, the copper
pipe disposed in the first spacial area.
Description
FIELD OF THE INVENTION
The present invention relates to a foamed thermal-insulating
material used in insulating devices such as refrigerators,
freezers, etc. and to an insulated structure utilizing the foamed
thermal-insulating material.
BACKGROUND OF THE INVENTION
Recently, environmental issues such as the destruction of the ozone
layer and global warming, which are influenced by Chloro Fluoro
Carbons (CFCs), are receiving close attention. For this reason,
reduction in the use of CFCs as a foaming agent has become a very
important issue.
Therefore, since hard urethane foam is the leading foamed
thermal-insulating material, it is proposed to use a hydrocarbon
foaming agent which does not include a halogen molecule.
However, a hydrocarbon is not easily applied as a foaming agent
because of combustibility safety, thermal-insulating efficiency
quality, and so on. Further, a foamed thermal-insulating material
made using a hydrocarbon as a foaming agent is less effective than
the foamed thermal-insulating material made by using the present
CFC11 foaming agent.
SUMMARY OF THE INVENTION
Concerning the above mentioned problem, the present invention aims
to provide the foamed thermal-insulating material and the insulated
structure filled with the foamed thermal-insulating material that
are not inferior to the present foamed thermal-insulating material
made by using the CFC11 foaming agent in terms of combustibility
safety, thermal-insulating efficiency quality, and so on, when a
hydrocarbon is applied as a foaming agent.
To achieve the above mentioned goal, the present invention aims to
restrain combustibility of the foamed thermal-insulating material
and to prevent the release of halides, which are a cause of acid
rain, by adding a non-halogenated organophosphorus compound as an
additive to the raw materials of the foamed thermal-insulating
material which includes a hydrocarbon foaming agent such as pentane
and/or cyclopentane.
In addition, a non-halogenated organophosphorus compound having a
molecular weight over 150 as an additive with an OH group as a
functional group is reacted and polymerized to an organic
polyisocyanates in order to eliminate the possibilities of phosphor
corrosion by free ionization to the metal pipes which are disposed
inside of the insulated structure and to eliminate the
possibilities of food contamination by phosphorus transfer through
the plastic board.
Also, organic polyisocyanates that have been polymerized by a
non-halogenated organophosphorus compound with active hydrogen are
used as the raw materials of the foamed thermal-insulating material
which includes a hydrocarbon such as pentane and/or cyclopentane as
a foaming agent, in order to restrain combustibility of the foamed
thermal-insulating material and to prevent the release of halides,
which are a cause of acid rain, caused by the burning of the foamed
material for disposal purposes. Further, this composition helps
eliminate the possibilities of phosphor corrosion by free
ionization to the metal pipes which are disposed inside of the
insulated structure, and helps eliminate the possibilities of food
contamination by phosphorus transfer through the plastic board
despite retaining a phosphor component in the urethane resin.
A Polyol component including at least 5% or more of
polyether-polyol, which is obtained from the additional
polymerization of ethylenediamine and alkylene-oxide with a
hydroxyl value of 350-650 mg KOH/g, is used as the raw materials
for the foamed thermal-insulating material which includes a
hydrocarbon such as pentane and/or cyclopentane as a foaming agent,
in order to improve mutual solubility between a polyol component
and a hydrocarbon foaming agent. This maintains the quality of the
foamed thermal-insulating material by having a foaming agent
equally soluble to the raw material components. Further, this
composition improves the insulating efficiency of the foamed
thermal-insulating material by raising the addition ratio of a
hydrocarbon foaming agent to lower amounts of a co-foaming agent,
such as water, and by lowering the ratio of carbonic acid gas,
which has a higher gaseous thermal conductivity, among other gas
components being retained in the bubbles of the foamed
thermal-insulating material.
An antioxidant catalyst is used as a catalyst for the raw materials
of the foamed thermal-insulating material which includes a
hydrocarbon such as pentane and/or cyclopentane as a foaming agent.
This catalyst is used in order to achieve a low-density foam and to
increase foaming efficiency by sharply lowering catalytic
activation from the beginning to the middle stages of the reaction
and by raising the temperature of the pre-mixed raw materials from
5 to 10 degrees C. At this point, due to the use of an antioxidant
catalyst, the foamed thermal-insulating material has a good
reaction balance since catalytic activation from the beginning to
the middle stages of the reaction is distinctly lowered and the
cream time and the gel time will not be extremely shortened in
spite of the raised temperature of the raw materials.
Also, the problem of filling the cabinets up with foam is
eliminated because the foam viscosity is lowered and the
uprising-process of foam viscosity is moderated by lowering
catalytic activation in the early stage of reaction to make more
foam available. In addition, a large amount of catalyst is not
needed and a usual prescription of additive is maintained.
Accordingly, there are no filling problems such as found with cure
and adhesive foams, and a foamed thermal-insulating material with
high quality is obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an insulated structure with a
portion in section according to an illustrated operation of the
present invention; and
FIG. 2 is a cross-sectional view of the insulated structure
according to the illustrated operation of the present
invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following text, referring to FIGS. 1 and 2, is an explanation
of the operation of the present invention.
Referring to FIG. 1, the insulated structure (1) is formed into the
space between a plastic board (2), which is made of material such
as ABS, and a metal plate (3) by injection of a foamed
thermal-insulating material created by foaming which is made of
hard urethane foam (4). The copper pipes (5), which have
circulating refrigerant, are disposed in the foamed
thermal-insulating material (4).
Table 1 indicates a prescribed combination ratio of the raw
materials of the foamed thermal-insulating material (4) for
illustrated operation 1 and illustrated comparisons 1, 2, and
3.
TABLE 1 ______________________________________ Illustrated
Illustrated Illustrated Illustrated Operation Comparison Comparison
Comparison 1 1 2 3 ______________________________________
Prescribed raw materials and Combination weight ratio Polyol 100
100 100 100 Foam Stabilizer 3 3 3 3 Catalyst 2 2 2 2 Foaming Agent
15 15 15 0 Foaming Agent 1 1 1 1 B Foaming Agent 0 0 0 32 C
Additive A 8 0 0 0 Additive B 0 0 5 0 Isocyanate Component 135 135
135 135 Analyzed Outcome Burning Time 75 40 85 70 (second)
Corrosion of no no no the Copper corrosion corrosion corrosion
corrosion Pipes Phosphorus Transfer no no no through transfer
transfer transfer transfer Plastic Board
______________________________________
Referring to Table 1
1) polyol is an aromatic amine polyether-polyol with a hydroxyl
value of 460 mg KOH/g
2) the foam stabilizer (the surfactant agent) is a silicon surface
active agent F-335 from Shinetsu Kagaku Kogyo Kabushiki Gaisha
3) the catalyst is Kaoraizer No. 1 from Kao Company
4) the foaming agent A is cyclopentane
5) the foaming agent B is pure water
6) the foaming agent C is CFC11
7) the additive A is a phosphorus organic compound having
dibutyl-hydroxymethyl-phosphonate
8) the additive B is tris (2-chlorethyl) phosphate which includes a
halogen
9) the isocyanate component is an organic polyisocyanates having a
crude MDI with amine equivalent 135
In illustrated operation 1, each raw material such a polyol, a foam
stabilizer, a catalyst, the foaming agent A, the foaming agent B,
and the additive A, is mixed according to a prescribed combination
ratio and is compounded as a pre-mix component. Then, the insulated
structure (1) is formed by injection of this compounded pre-mix
component and an isocyanate component, which are mixed by a
prescribed combination ratio and are foamed in a high-pressure
foaming machine, into the space between the plastic board (2) and
metal plate (3) with a disposition of copper pipes (5).
In illustrated comparison 1, each raw material such as polyol, a
foam stabilizer, a catalyst, the foaming agent A, and the foaming
agent B, is mixed according to a prescribed combination ratio and
is compounded as a pre-mix component. Then, the insulated structure
(1) is formed by injection of this compounded pre-mix component and
an isocyanate component, which are mixed by a prescribed
combination ratio and are foamed in a high-pressure foaming
machine, into the space between the plastic board (2) and metal
plate (3) with a disposition of copper pipes (5).
In illustrated comparison 2, each raw material such as polyol, a
foam stabilizer, a catalyst, the foaming agent A, the foaming agent
B, and the additive B, is mixed according to a prescribed
combination ratio and is compounded as a pre-mix component. Then,
the insulated structure (1) is formed by injection of this
compounded pre-mix component and an isocyanate component, which are
mixed by a prescribed combination ratio and are foamed in a
high-pressure foaming machine, into the space between the plastic
board (2) and metal plate (3) with a disposition of copper pipes
(5).
In illustrated comparison 3, each raw material such as polyol, a
foam stabilizer, a catalyst, the foaming agent B, and the foaming
agent C, is mixed according to a prescribed combination ratio and
is compounded as a pre-mix component. Then, the insulated structure
(1) is formed by injection of this compounded pre-mix component and
an isocyanate component, which are mixed by a prescribed
combination ratio and are foamed in a high-pressure foaming
machine, into the space between the plastic board (2) and metal
plate (3) with a disposition of copper pipes (5).
Illustrated comparison 1 uses no additives. Illustrated comparison
2 added tris (2-chlorethyl) phosphate including a halogen as an
additive. Illustrated comparison 3 uses CFC11 as a foaming
agent.
The degree of combustibility for each foamed thermal-insulating
material (4) is shown in Table 1 under the heading "Analyzed
Outcome". The degree of combustibility is provided as a burn time,
measured in seconds, listed in a combustibility test item of
JIS-A9514.
The Analyzed Outcome of Table 1 also indicates whether corrosion of
the copper pipes (5) and phosphorus transfer through the plastic
board (2) occurs when the insulated structure (1) has been operated
for 3 months under the conditions of 40.degree. C. and 95%RH.
As clearly shown in the Analyzed Outcome of Table 1, the
combustibility for the resin part of the foamed thermal-insulating
material (4) is restrained when dibutyl-hydroxymethyl-phosphonate
(Additive A) (the non-halogenated organophosphorus compound which
has a molecular weight over 224 as an additive with an OH group as
a functional group) is used as an additive (illustrated operation
1). Further, the degree of combustibility becomes almost same as
that of illustrated comparison 3 (using CFC11 as the foaming agent)
even if the hydrocarbon cyclopentane, which is combustible, is used
as the foaming agent.
As a result, it eliminates the risk of fire or spread of fire,
contributes to the solution of global environmental issues such as
the destruction of the ozone layer, and generally makes the product
available to be safely used. In addition, phosphor corrosion by
free ionization to the copper pipes (5) is eliminated since
dibutyl-hydroxymethyl-phosphonate, which has a molecular weight
over 224 with an OH group as a functional group, is reacted and
polymerized to an organic polyisocyanates. Even under high humidity
conditions, where moisture penetration from the outside attaches to
the copper pipes to cause phosphor corrosion, there aren't any
corrosion problems. In other words, the restraint of free
ionization of phosphor due to the polymerization enhances product
reliability for long term use.
Furthermore, since there is no phosphorus transfer through the
plastic board (2), there are no worries of food contamination, and
food can be preserved for extended periods of time.
On the other hand, illustrated comparison 1, which uses no
additives, is not suitable because of the increase of the
combustibility speed when it is compared to illustrated comparison
3, which uses CFC 11 as the foaming agent. Also, illustrated
comparison 2, which added tris (2-chlorethyl) phosphate including a
halogen as an additive, is not suitable because of the corrosion of
the copper pipes (5) and the phosphorus transfer through the
plastic board (2).
The following is an explanation pertaining to illustrated operation
2 of the invention.
Table 2 indicates a prescribed combination ratio of the raw
materials of the foamed thermal-insulating material (4) for
illustrated operation 2 and illustrated comparisons 4, 5, and
6.
TABLE 2 ______________________________________ Illustrated
Illustrated Illustrated Illustrated Operation Comparison Comparison
Comparison 2 4 5 6 ______________________________________
Prescribed raw materials and Combination weight ratio Polyol 100
100 100 100 Foam Stabilizer 3 3 3 3 Catalyst 2 2 2 2 Foaming Agent
15 15 15 0 Foaming Agent 1 1 1 1 B Foaming Agent 0 0 0 32 C
Isocyanate Component A 148 0 0 0 Isocyanate Component B 0 135 0 135
Isocyanate Component C 0 0 143 0 Analyzed Outcome Burning Time 75
40 85 70 (second) Corrosion of no no no the Copper corrosion
corrosion corrosion corrosion Pipes Phosphorus no no no Transfer
transfer transfer transfer transfer through Plastic Board
______________________________________
Referring to Table 2
1) polyol is an aromatic amine polyether-polyol with a hydroxyl
value of 460 mg KOH/g
2) the foam stabilizer is a silicon surface active agent F-335 from
Shinetsu Kagaku Kogyo Kabushiki Gaisha
3) the catalyst is Kaoraizer No. 1 from Kao Company
4) the foaming agent A is cyclopentane
5) the foaming agent B is pure water
6) the foaming agent C is CFC11
7) the isocyanate component A is an organic polyisocyanates having
a crude MDI with amine equivalent 135, which is previously
polymerized with combination ratio 5% of a phosphorus organic
compound having dibutyl-hydroxymethyl-phosphonate with a molecular
weight 224 and a hydroxyl value of 250 mg KOH/g
8) the isocyanate component B is an organic polyisocyanates having
a crude MDI
9) the isocyanate component C is an organic polyisocyanates having
combination ratio of 5% of tris (2-chlorethyl) phosphate including
a halogen
In illustrated operation 2, each raw material such as polyol, a
foam stabilizer, a catalyst, the foaming agent A, and the foaming
agent B, is mixed according to a prescribed combination ratio and
is compounded as a pre-mix component. Then, the insulated structure
(1) is formed by injection of this compounded pre-mix component and
an isocyanate component A, which are mixed by a prescribed
combination ratio and are foamed in a high-pressure foaming
machine, into the space between the plastic board (2) and metal
plate (3) with a disposition of copper pipes (5).
In illustrated comparison 4, each raw material such as polyol, a
foam stabilizer, a catalyst, the foaming agent A, and the foaming
agent B, is mixed according to a prescribed combination ratio and
is compounded as a pre-mix component. Then, the insulated structure
(1) is formed by injection of this compounded pre-mix component and
an isocyanate component B, which are mixed by a prescribed
combination ratio and are foamed in a high-pressure foaming
machine, into the space between the plastic board (2) and metal
plate (3) with a disposition of copper pipes (5).
In illustrated comparison 5, each raw material such a polyol, a
foam stabilizer, a catalyst, the foaming agent A, and the foaming
agent B, is mixed according to a prescribed combination ratio and
is compounded as a pre-mix component. Then, the insulated structure
(1) is formed by injection of this compounded pre-mix component and
an isocyanate component C, which are mixed by a prescribed
combination ratio and are foamed in a high-pressure foaming
machine, into the space between the plastic board (2) and metal
plate (3) with a disposition of copper pipes (5).
In illustrated comparison 6, each raw material such as polyol, a
foam stabilizer, a catalyst, the foaming agent B, and the foaming
agent C, is mixed according to a prescribed combination ratio and
is compounded as a pre-mix component. Then, the insulated structure
(1) is formed by injection of this compounded pre-mix component and
an isocyanate component B, which are mixed by a prescribed
combination ratio and are foamed in a high-pressure foaming
machine, into the space between the plastic board (2) and metal
plate (3) with a disposition of copper pipes (5).
Illustrated operation 2 uses isocyanate component A and
cyclopentane as the foaming agent. Illustrated comparison 4 uses
the isocyanate component B instead of the isocyanate component A.
Illustrated comparison 5 uses the isocyanate component C instead of
the isocyanate component A. Illustrated comparison 6 uses CFC11 as
a foaming agent instead of cyclopentane and the isocyanate
component B instead of the isocyanate component A.
The degree of combustibility for each foamed thermal-insulating
material (4) is shown in Table 2 under the heading "Analyzed
Outcome". The degree of combustibility is provided as a burn time,
measure in seconds, listed in a combustibility test item of
JIS-A9514.
The Analyzed Outcome of Table 2 also indicates whether corrosion of
the copper pipes (5) and phosphorus transfer through the plastic
board (2) occurs when the insulated structure (1) has been operated
for 3 months under the conditions of 40.degree. C. and 95%RH.
As clearly shown in the Analyzed Outcome of Table 2, the
combustibility for the resin part of the foamed thermal-insulating
material (4) is restrained when an organic polyisocyanates with a
crude MDI which has been polymerized by
dibutyl-hydroxymethyl-phosphonates (isocyanate component A) (the
non-halogenated organophosphorus compound which has a molecular
weight over 224 as an additive with active hydrogen) is used as the
isocyanate component (illustrated operation 2). Further, the degree
of combustibility becomes almost same as that of illustrated
comparison 6 (using CFC11 as the foaming agent) even if the
hydrocarbon cyclopentane, which is combustible, is used as the
foaming agent.
As a result, it eliminates the risk of fire or spread of fire,
contributes to the solution of global environmental issues such as
the destruction of the ozone layer, and generally makes the product
available to be safely used. In addition, phosphor corrosion by
free ionization to the copper pipes (5) is eliminated since
dibutyl-hydroxymethyl-phosphonate is previously reacted and
polymerized to an organic polyisocyanates. Even under high humidity
conditions, where moisture penetration from the outside attaches to
the copper pipes to cause phosphor corrosion, there aren't any
corrosion problems. In other words, the restraint of free
ionization of phosphor due to the pre-polymerization to an organic
polyisocyanates enhances product reliability for long term use.
Furthermore, since there is no phosphorus transfer through the
plastic board (2), there are no worries of food contamination, and
food can be preserved for extended periods of time.
On the other hand, illustrated comparison 4, which uses an organic
polyisocyanates having a crude MDI as the isocyanate component, is
not suitable because of the increase of the combustibility speed
when it is compared to illustrated comparison 6, which uses CFC 11
as the foaming agent. Also, illustrated comparison 5, which uses an
organic polyisocyanates having a combination ratio of 5% of tris
(2-chlorethyl) phosphate including a halogen as the isocyanate
component, is not suitable because of the corrosion of the copper
pipes (5) and the phosphorus transfer through the plastic board
(2).
The following is an explanation pertaining to illustrated operation
3 of the invention.
Table 3 indicates a prescribed combination ratio of the raw
materials of the foamed thermal-insulating material (4) for
illustrated operation 3 and illustrated comparisons 7 and 8.
TABLE 3 ______________________________________ Illustrated
Illustrated Illustrated Operation 3 Comparison 7 Comparison 8
______________________________________ Prescribed raw materials and
Combination weight ratio Polyol A 20 0 0 Polyol B 80 100 100 Foam
Stabilizer 1.5 1.5 1.5 Catalyst 2 2 2 Foaming Agent A 28 28 18
Foaming Agent B 0.5 0.5 1.5 Isocyanate Component 127 127 133
Analyzed Outcome Thermal Conductivity 0.0185 0.0185 0.0195 (W/mK)
Carbonic acid gas in the 50-60 50-60 70-80 foam Density Maximum 36
40 *1 36 (kg/cm3) Minimum 35 32 *2 35 Filling property of foam good
*1 leak good into the insulated box *2 unfilled structure
______________________________________
Referring to Table 3
1) polyol A is a polyether-polyol which is obtained from the
additional polymerization of ethylenediamine and propylene-oxide
with a hydroxyl value of 400 mg KOH/g
2) polyol B is an aromatic amine polyether-oxide with a hydroxyl
value of 460 mg KOH/g
3) the foam stabilizer is a silicon surface active agent F-335 from
Shinetsu Kagaku Kogyo Kabushiki Gaisha
4) the catalyst is Kaoraizer No. 1 from Kao Company
5) the foaming agent A is n-pentane
6) the foaming agent B is pure water
7) the isocyanate component is an organic polyisocyanates having a
crude MDI with amine equivalent 135
In illustrated operation 3, each raw material such as polyol A,
polyol B, a foam stabilizer, a catalyst, the foaming agent A, and
the foaming agent B is mixed according to a prescribed combination
ratio and is compounded as a pre-mix component. Then, the insulated
box structure (1) is formed by injection of this compounded pre-mix
component and an isocyanate component, which are mixed by a
prescribed combination ration and are foamed in a high-pressure
foaming machine, into the space between ABS material (2) inside the
box and metal plate (3) outside the box.
In illustrated comparison 7, each raw material such as polyol B, a
foam stabilizer, a catalyst, the foaming agent A, and the foaming
agent B, is mixed according to a prescribed combination ratio and
is compounded as a pre-mix component. Then, the insulated box
structure (1) is formed by injection of this compounded pre-mix
component and an isocyanate component, which are mixed by a
prescribed combination ratio and are foamed in a high-pressure
foaming machine, into the space between ABS material (2) inside the
box and metal plate (3) outside the box.
In illustrated comparison 8, each raw material such as polyol B, a
foam stabilizer, a catalyst, the foaming agent A, and the foaming
agent B, is mixed according to a prescribed combination ratio and
is compounded as a pre-mix component. Then, the insulated box
structure (1) is formed by injection of this compounded pre-mix
component and an isocyanate component, which are mixed by a
prescribed combination ratio and are foamed in a high-pressure
foaming machine, into the space between ABS material (2) inside the
box and metal plate (3) outside the box.
As shown in Table 3, neither illustration comparison 7 nor
illustrated comparison 8 use ethylenediamine polyether as the
polyol, however, illustrated comparison 8 increased the amount of
pure water as a co-foaming agent.
Distinctive outcomes of thermal conductivity and density of the
thermal-insulating material for illustrated operation 3,
illustrated comparison 7 and illustrated comparison 8 are shown in
Table 3.
As clearly shown in the Analyzed Outcome of Table 3, the density
quality for the foamed thermal-insulating material of illustrated
operation 3, which is foamed in a high-pressure foaming machine, is
maintained at a proper level when n-pentane, which has poor mutual
solubility, is utilized as a foaming agent. Therefore, the
insulated box structure with the foamed thermal-insulating material
according to illustration operation 3 produces the same excellent
quality as the foamed thermal-insulating material using CFC11 as
the foaming agent, which is halogenated hydrocarbon foaming
agent.
Polyether-polyol, which has a good mutual solubility to a
hydrocarbon foaming agent and is equally soluble in the raw
material components, is obtained from the additional polymerization
of ethylenediamine and propylene-oxide with a hydroxyl value of 400
mg KOH/g and added as a part of the polyol components. Therefore,
problems such as separation of a hydrocarbon foaming agent in the
material tank of a high-pressure foaming machine is eliminated.
Also, the foamed thermal-insulating material with a proper quality
level is obtained by raising the addition ratio of a hydrocarbon
foaming agent to lower the amount of co-foaming agent, such as
water, which lowers the amount of carbonic acid gas, which has a
higher gaseous thermal conductivity, among the other gas components
being retained in the bubbles of the foamed thermal-insulating
material. This is apparent in comparing illustrated operation 3
with illustrated comparison 7.
As a result, the foamed thermal-insulating material produced per
illustrated operation 3 contributes to the solution of global
environmental issues, such as the destruction of the ozone layer,
by using a hydrocarbon foaming agent which has a zero coefficient
in the destruction of the ozone layer. Moreover, it also
contributes to improve the quality and to save energy by having the
same excellent insulating efficiency as that of the present
halogenated hydrocarbon foaming agent.
In addition, the foamed thermal-insulating material maintains a
proper quality level during the production process and provides an
excellent quality in the insulated box structure, maintaining the
same excellent insulating efficiency as that of the present
halogenated hydrocarbon foaming agent.
As shown in illustrated comparison 7, when the same amount of the
hydrocarbon foaming agent used in illustrated operation 3 is used
without a polyether of ethylenediamine being added, the density of
the thermal-insulating material foamed in a high-pressure foaming
machine is not maintained and problems such as a leak and unfilled
parts of the foamed thermal-insulating material in the insulated
box structure occur. Also, as shown in illustrated comparison 8,
when water as a co-foaming agent is increased, there is little
improvement of insulating efficiency due to the increase in the
amount of carbonic acid gas in the bubbles.
The following is an explanation pertaining to illustrated
operations 4-7 of the invention.
Table 4 indicates a prescribed combination ratio of the raw
materials of the foamed thermal-insulating material (4) for
illustrated operations 4-7 and illustrated comparisons 9-12.
TABLE 4 ______________________________________ Illustrated
Operation Illustrated Comparison 4 5 6 7 9 10 11 12
______________________________________ Prescribed raw materials and
Combination weight ratio Polyol 100 100 100 100 100 100 100 100
Foaming 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Stabilizer Catalyst No. 31
1.5 1.0 -- -- 2.2 2.2 1.7 1.7 Catalyst No. 55 1.5 2.0 3.0 3.0 -- --
-- 0.5 Water 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Cyclopentane 18 18 18
18 18 18 18 18 Isocyanate 148 148 148 148 148 148 148 148 Pre-mix
Tem- 27 27 27 32 22 27 27 27 perature (.degree.C.) Reactivity (GT)
30 32 35 30 30 25 30 28 (second) Free Density 27.0 27.0 27.0 26.3
28.5 27.0 27.0 27.0 (Kg/m3) Quality of the Insulated box structure
Expansion of 2.0 2.0 2.0 2.0 3.0 3.0 7.0 4.0 insulated box (%)
Peel-off of no no no no no no yes no board after cold thermal
cycles Filling property good good good good good poor good good of
foam into the insulated box
______________________________________
Referring to Table 4
1) polyol is a compound of aromatic amine polyether-polyol and
poly-ether-polyol of ethylenediamine with a total hydroxyl value of
460 mg KOH/g
2) the foam stabilizer is a silicon surface active agent F-335 from
Shinetsu Kagaku Kogyo Kabushiki Gaisha
3) the catalysts are Kaoraizer No. 31 and No. 55 from Kao
Company
4) the foaming agent is cyclopentane
Each raw material is mixed according to a prescribed combination
ratio and is compounded as a pre-mix component.
In addition, the isocyanate component is an organic polyisocyanates
having a polymeric MDI with amine equivalent 135.
The insulated box structure (1) is formed by injection of this
compounded pre-mix component and an isocyanate component, which are
mixed by a prescribed combination ratio and are foamed in a
high-pressure foaming machine, into the space between ABS material
(2) inside the box and metal plate (3) outside the box.
The pre-mix component, which is mixed with a foaming agent,
polyether-polyol, and a mixed material as a helping agent, is
formed by using a static mixer.
The four test measurements provided in Table 4 are as follows:
1) the free density in Kg/m.sup.3 of the urethane foam which is
foamed according to prescribed urethane raw material data in Table
4;
2) the filling property of the foam into the insulated box
structure which is foamed at the free density aiming for a core
density of 34 kg/cm.sup.3 ;
3) the expansion of the insulated box structure which measures the
degree of cure foams at the time of the operation; and
4) the peeling off of the board after thermal and cold cycles,
which is the peeling off of urethane foam from the ABS board inside
the box and metal board outside the box after the insulated box
structure has been operated in 5 cold and thermal cycles of
30.degree. C. for 12 hours and 60.degree. C. for 12 hours.
Each result, such as the case without an increase of raw material
temperature, the case without applying Kaoraizer No. 55 which is an
antioxidant catalyst, and the case using Kaoraizer No. 55 with
under 50% by weight of a catalyst component, are shown in Table 4
as illustrated comparisons 9-12.
As is clearly shown in the "Quality of the Insulated box structure"
of Table 4, when Kaoraizer No. 55 with under 50% by weight of a
catalyst component is applied, the problems of filling the
insulated box with the foam and reactivity are eliminated even when
a low-density foam is set and the temperature of the pre-mixed raw
materials is raised from 5 to 10 degrees centigrade, because an
antioxidant catalyst, which is comprised of both a first tertiary
amine polymer and a second tertiary amine polymer with over 50% by
weight of a catalyst component being partially or entirely
neutralized by carboxylic acid, is used as a catalyst
component.
Therefore, when cyclopentane is used as a foaming agent, lowering
the foam density becomes possible by raising the temperature of the
raw materials without a large change of a present prescription
instead of developing new mutual soluble raw materials.
When an antioxidant catalyst, which is comprised of both a first
tertiary amine polymer and a second tertiary amine polymer with
under 50% by weight of a catalyst component being partially or
entirely neutralized by carboxylic acid, is used as a catalyst
component, there are problems of worse cure and adhesive foams
since the adjustment of reactivity becomes necessary due to a
decrease of catalyst amount. Also, early reactivity occurs and the
filling property of the foam into the insulated box structure
becomes worse without the adjustment of reactivity.
As a result, cyclopentane (one of a hydrocarbon being used as a
urethane foaming agent), which helps to solve global environmental
issues because of its zero coefficient to the destruction of the
ozone layer and because of its small influences to global warming,
is used without a large prescription change in order to provide the
high quality foamed thermal-insulating material which has many
kinds of foam characteristics presently being used and also to
provide the high quality insulated box structure in which the
foamed thermal-insulating material is filled by injection.
Possible Production Use:
As explained, the foamed thermal-insulating material and the
insulated structure filled up with the foamed thermal-insulating
material in the present invention are not inferior to the present
foamed thermal-insulating material made by a CFC11 foaming agent in
terms of combustibility safety, thermal-insulating efficiency
quality, etc., when a hydrocarbon is applied as a urethane foaming
agent, and also helps to solve global environmental issues because
of its zero coefficient as to the destruction of the ozone layer
and because of its negligible influence on global warming.
* * * * *